Petroleum product and process of making the same.



R. DE M. TAVEAU.

PETROLEUM PRODUCT AND PROCESS OF'MAKING THE SAME.

APPLICATION FILED IuLY 6.1914.

1 ,271,387. Patented July 2, 1918..

2 SHEETS-SHEET I.

.Ffa I- (u: y N A'I-roRNEY n Patented July 2, 1918 2 SHEETS-SHEET 2.

WITNESSES 6PM MMT AlrroRNEY UNITED sTATEs PATENT oEEIoE.

RENE DE M. TAVEA'U, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNOR TO THE ATLANTIC REFINING- COMPANY, OF PHILADELPHIA, PENNSYLVANIA, A CORPORATION OF PEN N SYLVANI;

PETROLEUM PRODUCT AND PROCESS OF MAKING THE SAME.

Specification of Letters Patent.

Patented July 2,- 191s.

Application filed July 6, 1914. Serial No. 849,119.

A l the following is a speci cation.

Myinventlon resides in a process of treating certain products resulting `from acid treatment of petroleum, petroleum distillates or residua remaining after distillation of petroleum for recovering or deriving therefrom an emulsion, asphalt, oil, sulfonic acids or sulfonates; and my invention resides in these products resulting` from' such process.

Whenevercrude petroleum, petroleumv distillate or the residuum remaining after distillation of crude petroleum is brought into contact with concentrated sulfuric acid, 50@ B, or stronger, including fuming sulfuric acid, or some other suitable sulfonating agent, as chlor'sulfonic acid, amore or less extensive reaction takes place in which the asphaltic constituents or asphalt forming constituents and oil of the crude petroleum, distillate or residuum are chemically or physically associated with the acid forming a sludge, commonly called acid sludge, which separates by gravity from and can readily be removed from the remainder of the mass. wWhen this acid sludge is diluted with hot Water or treated With steam a. more or less complete separation is effected into diluted sulfuric acid and hydrocarbons and sulfonated hydrocarbons. With sludges from heavy hydrocarbons (such as paratlin oils, spindle or lubricating oils), treatment with steam effects a separation into three distinct layers, an upper oily layer, a middle layer consisting of acid tar comprising dilute sulfuric acid, hydrocarbons and. sulfonated hydrocarbons, and a lower layer of diluted sulfuric acid. With acid sludges from light hydrocarbons'the, same separatior takes place when water is added Without the use of steam. lVith these last mentioned acid sludges little or no acid tar is formed. lVhen cold water is used on'the acid sludges from heavy hydrocarbons disintegration takes place Without separation into layers, the product in such case being similar in consistency to dough, and is not, strictly speaking, an acid tar, (though when fused separation takes place into three layers, the middle one of which is acid tar) because differing therefrom physically as to struc,

ture and, it isbelieved, differing chemically.

This dough-like product may be treated as hereinafter described, for separation of sulfonic acids or sulfonates and asphalt and oil. 4It has heretofore been common practice -to throw away or burn the above-mentioned -acid tar which when Warm is a thick Huid,

but when cooled or at ordinary temperatures is often a solid, sometimes called acid By my invention, however, I treat such acid tar, particularly When resulting from the aforementioned heavier distillate acid sludges to produce asphalt, oil, sulfonic acids or sulfonates, and emulsions.

This acid tar produced from any of the sludges as above described, consists of asphalt or asphalt forming material, oil, sullfonic acids, sulfuric acid originally used in concentrated form, sulfurous acid, Water, and sulfates 'of organic nitrogen bases.

The acid tar or asphaltic residue from the acid sludge is first preferably though not necessarily finely divided in any Way, as'by granulation. ranulation may be accomplished bybring'ing `the thick fluid mass while Warm into contact with cold Water and breaking up the now solid tar, as by Archimedean screw, into small particles or granules. At this stage the acid tar may be furi ther freed of sulfuric and sulfurous acids by Washing with Water.

The material is emulsied by mixing with Water to which there has been previously or simultaneously added, or to Which there is added after mixture With the preferably i and all or part of the sulfonic acids. .The

liquor is preferably simultaneouslyagitated, as by blowing' air therethrough or by stirring to speed the action, The liquor at the beginv Y and then distilled. The benzol orother solning of this treatment fis preferablyrelatively cool, as, for example, at 90 degrees Fahrenheit, more or less, and as the chemie cal re-action and emulsifying action proceed or near'completion may be raised'to higher temperature, as for example, 150 degrees Fahrenheitrmore or less. For a charge of approximately vthirty-ve tons of acid coke three` hours, more or'less, suflice to emulsify the same.

kept warm As a resultof 'the -i aforementioned reac? tions sodium (potassium, ammonium, lithium or other); sulfonates are formed, and these sulfonates act as emulsifying agents for those asphaltic and other compounds present. The result is an emulsion of the asphaltic and oily constituents of the acid tar, which-'will not vbreak -or separate at ordinary temperatures and may b e used for purposes later described.

Having producedthe emulsion as above described, the same is brought, in approxiym'ately three hours'more'for a charge of approximately thirty-five tons, y to approxi-v mately 212o F. for ashorttime, as by. injecting steam into the emulsion, the temperature of the emulsion being raised to 212 de- If neces- When subjected to such high temperature the emulsion will break or separate. The

nowfbrokenv emulsion is then allowed to stand for fourV hours, more or less', and is i until separation into layers takes place. v Y The emulsion thenseparates into two layers for masses;A an laqueous lower mass or layer consisting' of water, sodium `orI other" 'sulfonates insolution in the water, sodium or other sulfate and 'sulite in solution in the water, an'd some small amount of asphaltic material remaining in the emulsied state; and an oily upper' layer or mass of asphalt and oil, which is readily removed and constitutes one of my4 products,- or vwhich may be distilledto separate' from the asphalt any oil present, leaving asphalt as one of my products, the oil distillate being suitable for fuel or'other purpose.

Or the emulsion of the acid tar may bey agitated, as by blowing airtherethrough, in the presence of'benzol or other suitable lsolvent for the yasphalt and oil, and then allowed to stand or settle with the result that there is a separation, inn shorter time than in the case above described, a half hour, more or less, into two layers or masses; an

aqueous lowerlayer or mass consisting of water, sodium or other sulfate and sulfite in solution therein, andvsodium or other sulfonates insolution therein, there being practically no. asphalt or oil in this layer in this case; and an oily upper layer of asphalt and oil 'in solution in benzol or other solvent used. This upper layer is readily removed,

vent distils olf and is' collected and saved,

and the asphalt and oil remain in the still as residuum and constitute one of my products. Or by further distillation any oil present is distilled off leaving asphalt as one of my products, the oil distillate being used for any purpose, to which it is suitable, as, for-example, fuel, Y Y rl`he liquor of the lower layers or strata separated from the emulsion by either of the Or the liquor containing the sodium or other sulfonates may have added thereto other metal saltsv soluble in water which react with the sodium or other sulfonatesto produce insoluble sulfonates of the metal of the salt added, these insoluble sulfonates being precipitated and then readily separated from the remaining liquor by common methods. i

Or .the-'liquor containing the sodium or other sulfonates may be treated with dilute mineral acid, for example, sulfuric or hydrochloric acid, vcausing the precipitation of free sulfonic acids which may then readily be separated from the remaining liquor by common methods. And these recovered sul- Afonic acids may then be readily converted ing to the sulfonic acids so recovered the sodium compound or salt of some weaker facid, for example, sodium carbonate; or

sodium hydroxid may be added.

Orthe liquor containing the sodium or other sulfonates may be evaporated to dryness or nearly so and the residue treated with alcohol or any other suitable\solvent for the sodium or other sulfonates. The result is an alcoholic or other solution of such sulfonates which is readily separated from the residue consisting of sodium or'other sulfates and sulites. And -this residue will contain alsonon-asphaltic black powder of unknown composition and the asphalt which may have remained in the emulsified condition in the lower layer or stratum resulting from the first mentioned treatment of the emulsion. The solution ofthe sodium or other sulfonates in the alcohol or other solvent is then distilled, the alcohol or other -solvent distilling ofi and is collected and saved, leaving behindas residue the sodium lor other sulfonates.

The above-mentioned sulfonates and free sulfonic acids I believe are new compounds or products and they vary among themselves in composition.

The substance of dough-like consistency hereinbefore referred to as derived from cold water treatment of acid sludges of the The asphaltic material and oil of the upper layer may then be separated by distilling off the solvent; and by further dis- `tillatlon the oil is distilled of, leaving the asphalt. v

The lower layer containing the bulk of the sulfonic acids and dilute sulfuric acid may then be treated by removing the sulfuric acid and distilling oli' from the residue theV benzol or other solvent therein leaving a residue of sulfonic acids.

The asphalt produced by anyof the aforementioned modes of treatment -is a new y product or article of manufacture in that it more nearlyV resembles the natural asphalts than the artificial asphalts her'etofore'produced since it is much heavier and more brittle than such artificial asphalts, and is suitable, either by itself or with the oil separated therewith, for mixture with or modication of either natural asphalts or the -previously known artificial asphalts de-v rived from crude petroleum or petroleumv residuum, such mixtures being suitable forroong, paving, metal coatingT etc.

he emulsions herein-before -referred to may be caused to separate or break by subjecting the same to the action of a centrifu# gal machine. Or by adding alcohol, ether, benzol or some other solvent for one of the constituents-of the emulsion. Or by passing electric current therethrough, whereupon finely divided matter in suspension is coagu lated or comes together in masses, and so separates from the remainder of the mate-- rial.

When the emulsion has been produced by employment of sodium or otasslum or other borate,l and particularly 1fr the borate has been-l added in quantity greater thanv necessary to completely react with the sulfonic acids, the emulsion is a product which operates as a binder, and isaii egeellent binder for coal or coke in' the manufacture. of briquets. For further explanation of my invention reference may be had to the `accompanying drawings, in which:

Figure 1 is a diagrammatic chart of the principal features of my process.

Fig. 2v is a representation of apparatus which may be employed for treating acid tar.

The acid sludges harged into the vesselv 1 into which is elivered steam or hot water through the pipe 2 controlled by the valve 3. The application of the steam or hot water causes the disintegration into the acid tar and dilute sulfuric acid which latter is' drawn off through the pipe 4.- controlled by the valve 5. The acid tar is delivered through the valve 6 to the rotating Archimedean screw 7 in the trough 8 above which is disposed a pipe 9 toi-which water is delivered through the valvelO, the water being .sprinkled from the pipe upon the acid tar as it is advanced towardfthe" right by the screw. This causes the granulation of the acid tar which `is then delivered into the vessel 11 'into which water is delivered from any source as pipe 10a connecting with pipe 10. Vessel 11 communicatesthrough the pipe 12 controlled by valve 13 with the suction of a centrifugal pump 14 which delivers the granulated acid tar in water through the pipe 15 controlled by va1ve'16 into the treating tank 17. Through 'the pipe 18 controlled by valve 19 aqueous 4solution of sodium hydroxid or other material hereinbefore mentioned is delivered into tank 17. The mass is then agitated by compressed air delivered through the pipe 20 which is controlled b valve 21, the pipe 20 communieating with the pipes 22 extending into the tank 17 and deliverin lair into the liquid and agit-ating the same.- hrcugh the pipes 22, or other similar pipes, steam ma bedelivered from time to time into the liquid mass beginning at approximately 90 degrees'` Fahrenheit, to approximatel 150 degrees` Fahrenheit. During the 'app ication of the heat and agitationfanemlsion'is formed as described. At this stage the operation may be discontinued andthe valve 23 opened to draw the emulsion ofil through the pipe 24. The emulsion at these low temperatures and at lower temperatures remains as such and is suitable for use in that state, and is one of my products.V

Whenthe emulsion is not to be used as such it is raised in temperature, in the tank 17, before drawing off through valve 23, to substantially the boiling` point by introduction lof steam through the pipes 22. Vhen the mass reaches such temperature the emulsion is broken or is in such 'state that it will separate into layers. As soon as such temperature is reached the application of steam is discontinued. Separation now takes place into layers, the upper layer being a solution of asphaltic material in oil, and the lower layer an aqueoussolution of sulfuric acid `through pipe 24 to the sewer, or if required for deriving sulfonic products is delivered to a suitable vessel, not shown. After the aqueous solution of the lower layer has thus been drawn off, the asphaltic material and oil are drawn off through pipe 24A to a still, not shown, where the oil may be distilled 0E, leaving the asphalt as residue. l

lVhat I claim is: Y

y l. The method of producing an emulsion of asphaltic material, which consists in disintegrating acid sludge, removing the acid, neutralizing all or a part of the sulfonic acid content of the asphalticv residue in the presence of Water, and agitating the mass .at a temperature below emulsion breaking temperature.

2. The method of producing an emulsion of asphaltic material, which consists in treating acid sludge with steam or hot water to produce acid tar containing asphaltic material and sulfonic acids, neutralizing all or a part of the sulfonic acid content in the presence o\f water to form emulsifying `agents lconsisting of water. soluble sulfonates, agitating the mass, and subjecting said asphalltic material to said agents at a temperature below emulsion breaking temperature.

3. The method of producing an emulsion of material contained in acid sludge, which consists in treating acid sludge with steam or hot water, separating oil and acid, and

agitating the residual acid tar in the presence of water and alkali at a temperature below emulsion breaking temperature.

4. The method of emulsifying acid tar, which consists in neutralizing all ora part of the sulfonic acid content in the presence of water to form emulsifying agents consi sting of water soluble sulfonates, agitating the mass, and subjecting the same to said agents at a temperature below emulsion breaking temperature. Y

5. The method of emulsifying acid tar, which consists in subdividing the same, as by granulation, mixing the same with water,

agitating the mass in the presence of a ma' terial reacting with sulfonic acids of the acid tar to'form emulsifying agents consisting of water soluble sulfonates, and subjecting the mass to said agents at a temperature below emulsion breaking temperature.

6. The method of emulsifying acid tar, which consists in vmixing the same with` w ater, adding alkali, and agitating the mass at a temperature below emulsion breaking temperature.

7. The method of emulsifying the asphal-v tic component of material resulting from the treatment of petroleum or petroleum product with concentrated sulfuric acid, which consists in mixing the asphaltic material and the associated sulfonic acids in water, agitating the mass inthe presence of material neutralizing the remaining sulfuric acid and reacting with the sulfonic acids to produce an emulsifying agent consist-ing of water soluble sulfonates, and subjecting the mass to said agent at a temperature below emulsion breaking temperature. v

8. The methodof emulsifying acid tar, which consists in mixing the same with water having a. temperature below about 160 degrees Fahrenheit, agitating the mass in the presence of materialreacting with the. sulfonic acids to form an emulsifving agent consisting of Water solublev sulfonates, and subjecting the mass to said agent.

9. The method of producing asphaltic material from acid tar, which consists in emulsifying the acid tar, raising the temperature of the emulsion to substantially the boiling point, allowing` thc emulsion to separate into layers, and recovering the asphaltic material from one of said layers.l

10. The method of producing asphaltic material from acid tar, which consists in subjecting the acid tar to an aqueous solution of alkali, heating the mass to a temperature conducive to separation, allowing separation into layers, removing the asphalt and oil from one of said layers, and separating the asphalt from the oil by distillation.

11. The method of emulsifying asphaltic Amaterial or oil, which consists in subjecting the same in the presence of water to an emulsifying agent comprising water soluble sulfonates' derived from acid sludge.

12. The method of deriving sulfonic acids from acid tar, which consists in emulsifying the acid tar, causing the emulsion .to separate into layers one of which contains water soluble sulfonates, and treating the liquor of such layer with dilute mineral acld to pre- `cipitate free sulfonic acids.

13. The method of derlving sulfonic acids from acid tar, which consists in subjecting the acid tar to an aqueous solution of alkali, heating the mass to a temperature conducive to separation, allowing separation into layersone of which contains water soluble lsulfonates, and treating` the liquor containing saidsulfonates with dilutemineral acid to precipitate free sulfonic acids.v

, 14. The method of deriving sulfonates from acid tar, which consists 'in emulsifying i the acidA tar, causing the emulsion to separate into layers one of which contains water soluble sulfonates, adding dilute mineral acid to precipitate free sulfonic acids, and treating said free sulfonic acids with a reagent to produce sulfonates.

15.' The petroleum product consistingof a mixture of sulfonic acids derived from acid tar.

16. The petroleum product consisting of asphaltic material derived from acid tar.

17. The petroleum product consistingl of asphaltic material derived from acid tar and substantially free of sulfonic compounds.

18. The method of emulsifying acid tar residue of acid sludge remaining after'treatment of the same with hot water or steam,

which consists in subjecting such residue in' tar.

20. The petroleum product consisting of asphaltic material and oil derived fromacid tar and substantially free of sulfonic compounds.

21. `The petroleum product comprising a mixture of sulfonates derived from acid tar..

22. .The productv consisting of an emulsion of asphalticl .material derived from acid acids, which consists in producing a water -tar...

23. .The product consisting of an emulsion*of asphaltic material of acid tar in water containing `soluble salts of sulfonic acids of acid sludge.

24. The petroleum product consisting of asphaltic'material derived from an emulsion of acid tar.

25. The method of emulsifying asphaltic material or oil, which consists in agitatihg the same in water containing'an .emulsifying a ent comprising-'water soluble sulfonates erived from acldsludge at a tempera'- ture of substantially 90 degrees F., increasing thel `temperature to substantially 150; de-

grecs F., and thereafter reducing the tem- Peratllre. f

26. The method of producing asphaltic material from acid s1udge,' which consists in subjecting the acid sludge to Steam or hot Water to form acid tar, emulsifying the acid tar, breakingthe emulsion, and separating 27. material from acid sludge, 'which vconsists in disintegrating acid sludge, emulsifying a residue' containing the asphaltic material, break# ing the emulsion and allowin material from one of said layers.

. j Separation 1nto layers, and separating t e asphaltic 28. The method of producing asphaltic material from acid sludge, which consists in disintegrating acid sludge by subjecting the same to steam or hot water, separating the aqueous liquid and leaving a residue of acid tar containing sulfonic acids, mixing said residue with water, converting sulfonc acids into water soluble sulfonates, subjecting the asphaltic material to the emulsifying action of said sulfonates, breaking the emulsion and allowing the same `to separate into layers, and separating the asphaltic material from one of said layers.

29. The method of producing asphaltic material from acid sludge, which consists in disintegrating acid sludge by subjecting the same to steam or hot water, separating the aqueous liquid and leaving' a residue comprising asphaltic material, oil and sulfonic acids, convertin the lsulfonic acids into Water soluble sulonates, subjecting the asphaltic material and oil to the emulsiying action of said sulfonates, breaking the resulting emulsion and allowing it to separate into layers, recovering the asphaltic material and oil from one of said layers, and separating the asphalt from the oil by distillation.

30. The method of producing a water emulsion of acid tar containing sulfonic acids, which consists in mixing the same with water in the presence of a reagent producing with said sulfonic acids water soluble sulfonates.

31. The method of producing asphaltic material from acid tar containing sulfonic .disintegrating acid sludge, separati-ng the aqueous liquid and leaving a residue consistmg of a mixture of sulfonic acids and as-y phaltic material, and separating the asphaltic material from saidresidue.

33. The method of producing asphaltic material from acid sludge, which consists in disintegrating acid sludge, separatingc the aqueousl liquid, emulsifyin the resldue, breaking the emulsion and a lowing se aration into layers, and recovering the asp altlc material from one ofsaid layers.

34, The method of deriving sulfonatesy from` acid tar, which consists in treating the acid tarwith water and alkali to form an emulsion, causing the .emulsion to separate into layers, and separating Water soluble sul- .fonates from one of said v ayers.

35. The method of treating acid tar to produce asphaltic materialand sulionates,l which consists in granulatmg the acld tar,

emulsifying the same by agitating the granulated acid tar in the presence of Water and alkali at a `temperature suitable for emulsiication, breaking the emulsion and allowing the mass to separate into layers containing, respectively, asphaltic material and sulfonates inv solution.

36. rlhe method of producing asphaltic material, -which consists in disintegrating acid sludgeV by steam or hot Water, separating the resultant acid tar, suhjectingthe acid tar to an aqueous solution of alkali, heating the mass to a temperature conducive to separation, allowing separation into a plurality of masses, and separating the asphaltic material of one of said masses.

37. rlhe method of producing asphaltic i material, which consistsin disintegrating acid sludge with steam or hot' Water, separating the resultant acid tar, granulating thev acid tar, subjecting the acid tar'granules to an aqueous solution of'alkali, heating the mass to' a temperature conducive to' separation, allowing'separation into a plurality of layers., and separating the asphaltic material of onel of said layers.

In testimony whereof Ihave hereunto af- 'Xedmy signature in the presence oi'the two subscribing witnesses'.

RENE DE M. TAVEAU.

'Witnesses:

H. M. NICHOLS, F. C. RoBINsoN. 

